What determines the critical size for phase separation in LiFePO ₄ in lithium ion batteries?

LiFePO₄ characteristically shows a plateau voltage due to a two-phase (LiFePO₄/FePO₄) separation during the charge/discharge process in Li ion batteries. In this study, we clearly show that monodispersed nano-sized (about 10 nm) LiFePO₄ particles exhibit a complete single-phase reaction without showing any plateau voltage. Since the elastic strain due to lattice mismatch between LiFePO₄ and FePO ₄ would be easily released near the surface, elastic effects are usually expected to weaken, but, in contrast to this expectation, phase separation does not occur experimentally in such small nanoparticles. Consideration on the basis of only static thermodynamics is insufficient to explain why such a single-phase reaction occurs in nano-sized particles. In contrast, the mechanism of the single-phase reaction can be naturally understood, when we consider a kinetics concept based on the preferred wavelength for stable growth of the spinodal wave under such an elastic constraint.